US4826803A - Process for the production of a syngas conversion catalyst - Google Patents

Process for the production of a syngas conversion catalyst Download PDF

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US4826803A
US4826803A US07/124,843 US12484387A US4826803A US 4826803 A US4826803 A US 4826803A US 12484387 A US12484387 A US 12484387A US 4826803 A US4826803 A US 4826803A
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alkali metal
solution
composition
ruthenium
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Graham Butler
Malcolm P. Heyward
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BP PLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/0445—Preparation; Activation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/63—Platinum group metals with rare earths or actinides

Definitions

  • the present invention relates to a process for the production of an improved catalyst for use in the conversion of gaseous mixtures principally comprising carbon monoxide and hydrogen, hereinafter referred to as synthesis gas, to hydrocarbons of carbon number greater than one, in particular to aliphatic hydrocarbons in the gasoline boiling range, and to the use of the catalyst so-produced in the conversion of synthesis gas to the aforesaid hydrocarbons.
  • ruthenium has long been known to be one of the most active catalysts in the conversion of synthesis gas, the product, at moderate pressures and above, being high molecular weight paraffin waxes and, at low pressures, principally methane.
  • Several recent patent publications for example U.S. Pat. Nos. 4,042,614; 4,171,320; 4,206,134; 4,413,064 and 4,410,637 and GB No. -A-2119277, describe and claim the formation of different products from synthesis gas using catalysts containing ruthenium as an active component.
  • U.S. Pat. No. 4,042,614 describes a process for the selective synthesis of olefins from C 2 to C 10 chain length inclusive from synthesis gas using as catalyst ruthenium on a titanium-containing oxide support, wherein said titanium-containing oxide support is selected from the group consisting of TiO 2 , ZrTiO 4 , TiO 2 --carbon, TiO 2 --Al 2 O 3 , TiO 2 --SiO 2 , alkaline earth titanates, rare earth titanates and mixtures thereof.
  • U.S. Pat. No. 4,171,320 describes a process for the synthesis of olefins of from C 2 to C 5 chain length inclusive from synthesis gas using as catalyst ruthenium on a support selected from the group consisting of V 2 O 3 , Nb 2 O 5 , Ta 2 O 5 Al 2 O 3 -V 2 O 3 , Al 2 O 3 -Nb 2 O 5 , Al 2 O 3 -Ta 2 O 5 , SiO 2 -V 2 O 3 , SiO 2 -Nb 2 O 5 , SiO 2 -Ta 2 O 5 , V 2 O 3 -carbon, Nb 2 O 5 -carbon, Ta 2 O 5 -carbon, alkaline earth-group VB oxides, alkali metal-Group VB oxides, Group IVB-Group VB oxides and mixtures thereof.
  • U.S. Pat. No. 4,206,134 describes a process for the enhanced synthesis of C 2 -C 4 olefins with reduced production of methane from synthesis gas using as catalyst ruthenium on a managanese-containing oxide support, wherein said manganese-containing oxide support is selected from the group consisting of MnO, Al 2 O 3 -MnO, SiO 2 -MnO, MnO-carbon, Group IVB-manganese oxide, Group VB-manganese oxides, rare earth-manganese oxides and mixtures thereof.
  • U.S. Pat. No. 4,413,064 describes a process for the conversion of synthesis gas to a product high in straight chain paraffins in the diesel fuel boiling range from synthesis gas utilising a catalyst consisting essentially of cobalt, thoria or lanthana and ruthenium on an alumina support wherein said alumina is gamma-alumina, etaalumina or a mixture thereof, said catalyst being prepared by contacting finely divided alumina with
  • U.S. Pat. No. 4,410,637 describes a process for the preparation of a hydrocarbon mixture consisting substantially of C 5 -C 12 hydrocarbons from synthesis gas using a catalyst containing one or more of iron, nickel, cobalt, chromium and/or ruthenium and, as a carrier, magadite, a laminar crystalline silicate compound capable of absorbing metal ions or metal salts by intercalation.
  • Example 3 there is disclosed a catalyst prepared by impregnating ceric oxide with an aqeous solution of RuCl 3 .3H 2 O (ruthenium content 0.62% w/w).
  • the impregnated catalyst when used in the conversion of synthesis gas (Run 9) produces an undesirably high methane yield (35.7%) and a low selectivity (1.6%) to desirable olefins.
  • BP Case No. 5890 there is described a process for the production of a composition for use after reductive activation as a catalyst in the conversion of synthesis gas to hydrocarbons of carbon number greater than one, which composition has the formula:
  • A is an alkali metal
  • x is a number such that the valence requirements of the other elements for oxygen is satisfied
  • a is greater than zero and less than 1% w/w, based on the total weight of the composition
  • b is in the range from zero to 10% w/w. based on the total weight of the composition
  • an aqueous solution of the precipitant is added to an aqueous solution of water soluble salts of the metals.
  • the present invention provides a process for the production of a composition for use after reductive activation as a catalyst in the conversion of synthesis gas to hydrocarbons of carbon number greater than one, which composition has the formula:
  • A is an alkali metal
  • x is a number such that the valence requirement of the other elements for oxygen is satisfied
  • a is greater than zero and less than 5% w/w, based on the total weight of the composition
  • b is in the range from zero to 10% w/w, based on the total weght of the composition
  • a in the formula (1) is less than 1% w/w.
  • A is an alkali metal, which is preferably potassium.
  • the amount b of alkali metal is greater than zero and up to 5% w/w, even more preferably up to 2% w/w.
  • a solution or solutions of soluble compounds of the metals ruthenium and cerium, and optionally also an alkali metal is added to a solution of a precipitant comprising a carbonate and/or a bicarbonate and/or a hydroxide of an alkali metal or ammonium under conditions whereby there is formed a precipitate comprising ruthenium and cerium, and optionally also an alkali metal, in the form of compounds thermally decomposable to the metals and/or their oxides.
  • step (A) may be operated continuously by feeding simultaneously to a precipitation zone and mixing therein a solution or solutions of soluble compounds of the metals ruthenium and cerium, and optionally also an alkali metal, and a solution of the precipitant under conditions whereby there is formed a precipitate comprising ruthenium and cerium, and optionally also an alkali metal, in the form of compounds thermally decomposable to their oxides.
  • the precipitation zone may suitably take the form of a vessel provided with means for separately introducing a solution of soluble compounds of ruthenium and cerium, and optionally also alkali metal, and a solution of the precipitant, the means for separately introducing the solutions being so arranged as to achieve mixing of the solutions, agitation means, pH measuring means and means for continuously withdrawing the suspended precipitate, for example an overflow pipe.
  • the solution or solutions employed may be aqueous solutions.
  • the compounds of ruthenium and cerium, and optionally also the alkali metal compound, may be contained in separate solutions and added to the precipitant solution in any order or they may be contained in a single solution and thereby added together to the precipitant.
  • ruthenium in the form of the chloride because this is a commercially available form and cerium in the form of the nitrate, for example cerous nitrate.
  • cerous nitrate which contains rare earth metals other than carium, may be employed if desired.
  • the precipitant in step (A) may be a carbonate and/or a bicarbonate and/or a hydroxide of an alkali metal.
  • a pre-formed carbonate or bicarbonate it is possible to use the precursors of these salts, for example a water soluble salt and carbon dioxide.
  • urea which is thermally decomposable to carbon dioxide and ammonia, may be used.
  • b in the aforesaid formula (I) will have a value greater than zero, which value may be adjusted if desired by washing or addition of further alkali metal compound.
  • ammonium carbonate and/or bicarbonate and/or hydroxide may be employed as the precipitant, in which case the value of b in the catalyst asinitially produced will be zero, though this value may subsequently be adjusted if desired by addition of alkali metal.
  • ammonium bicarbonate optionally mixed with an alkali metal bicarbonate, for example potassium bicarbonate, is used as the precipitant.
  • the soluble compounds of the metals ruthenium and cerium may be brought together at a temperature in the range from 0° to 100° C.
  • the temperature is suitably in the range from 60° to 100° C., preferably from 80° to 100° C.
  • the temperature is suitably below 50° C., preferably below 30° C., for example ambient temperature.
  • Precipitation may suitably be effected at a pH greater than about 6, preferably in the range from 6 to 10.
  • the pH is substantially constant within the aforesaid range throughout the precipitation step.
  • a substantially constant pH may suitably be achieved by using a large excess of the precipitant, for example about seven times the theoretical stoichiometric amount required for complete precipitation.
  • a suitable buffer may be employed.
  • step (A) the solutions are preferably fed at a relative rate such as to achieve a substantially constant pH within the aforesaid ranges.
  • a substantially constant pH it may be desirable to further feed a solution of an inorganic base, for example aqueous ammonia.
  • the amounts of the ruthenium and cerium compounds and precipitant employed should be such as to satisfy the stoichiometric relationships in the formula (I).
  • the alkali metal content of the composition may be supplemented by further addition thereof, or reduced, for example by washing, at any subsequent point in the preparative process.
  • step (B) the precipitate obtained in step (A) is recovered.
  • This may suitably be accomplished by filtration but other methods for separating solids from liquids, for example centrifugation, may be employed.
  • wash the precipitate suitably with water, so as to remove unwanted residual soluble matter.
  • dry the precipitate suitably at a temperature below 180° C., for example about 100° to 150° C. It is possible that some thermal decomposition may occur in the drying step.
  • Thermally decomposable compounds comprised in the precipitate recovered in step (B) are preferably further thermally decomposed in a discrete step (C). This may suitably be accomplished by heating the precipitate, suitably in a non-reducing atmosphere, for example a stream of inert gas, such as nitrogen, at a temperature suitably in the range from 150° to 600° C.
  • a non-reducing atmosphere for example a stream of inert gas, such as nitrogen
  • composition of formula (I) In order to convert the composition of formula (I) into a catalyst for use in the conversion of syngas to hydrocarbons having a carbon number greater than 1, it is generally necessary to reductively activate the composition, suitably by contact at elevated temperature with a reducing gas, for example hydrogen, carbon monoxide or mixtures thereof.
  • a suitable reducing gas is for example hydrogen which may be diluted with an inert gas such as argon.
  • the conditions employed may suitably be a pressure in the range from 1 to 100 bar and a temperature in the range from 150° to 600° C. for a period of up to 24 hours or longer.
  • Reductive activation may be effected as a discrete step prior to use as a catalyst for the conversion of synthesis gas or it may be incorporated as a preliminary step into the synthesis gas conversion process, preferably the latter.
  • coprecipitated catalysts differ fundamentally from impregnated catalysts and that this difference is reflected in their catalytic performance.
  • the present invention also provides a process for the production of hydrocarbons having a carbon number greater than one from synthesis gas which process comprises contacting synthesis gas with a catalyst comprising a reductively activated composition having the formula (I) produced by the process of claim 1 at a temperature in the range from 190° to 400° C. and a pressure in the range from about 1 bar to 100 bar.
  • Reductive activation of the composition of formula (I) may be conducted either as a separate step outside the syngas conversion reactor, as a discrete step within the syngas conversion reactor prior to syngas conversion or within the syngas conversion reactor under syngas conversion conditions.
  • benefits can arise from periodically treating the catalyst with hydrogen. This may suitably be accomplished by shutting off the carbon monoxide feed from time to time during the process.
  • synthesis gas principally comprises carbon monoxide and hydrogen and possibly also minor amounts of carbon dioxide, nitrogen and other inert gases depending upon its origin and degree of purity.
  • Methods for preparing synthesis gas are established in the art and usually involve the partial oxidation of a carbonaceous substance, e.g. coal.
  • synthesis gas may be prepared, for example by the catalytic steam reforming of methane.
  • the carbon monoxide to hydrogen ratio may suitably be in the range from 2:1 to 1:6.
  • the ratio of the carbon monoxide to hydrogen in the synthesis gas produced by the aforesaid processes may differ from these ranges, it may be altered appropriately by the addition of either carbon monoxide or hydrogen, or may be adjusted by the so-called shift reaction well known to those skilled in the art.
  • the catalyst may be combined with an acidic component, for example either a zeolite or a pillared clay.
  • the zeolite or pillared clay may be either physically admixed with the composition to form an intimately mixed bed or may be separate therefrom, for example in the form of a split bed, the zeolite or pillared clay forming one portion of the bed and the catalyst another.
  • the zeolite or pillared clay may be mixed with the composition either before or after reductive activation.
  • the coprecipitation (step A) in the process for producing the composition of formula (I) may be performed in the presence of the zeolite or pillared clay, particularly when the precipitant is ammonium carbonate and/or bicarbonate and/or hydroxide.
  • a suitable zeolite is an MFI-type zeolite, for example ZSM-5 as described in U.S. Pat. No. 3,702,886, though other suitable high silica crystalline alumino- or gallo-silicate zeolites may be employed.
  • Suitable pillared clays are described for example in GB No. -A-2,059,408, U.S. Pat. Nos. 4,216,188, 4,248,739, 4,515,901 and 4,367,163.
  • a particularly suitable pillared clay is the silylated pillared clay described in our copending EP No. -A-0150898 (BP Case No. 6035). The aforesaid patent publications are incorporated by reference herein.
  • the temperature is preferably in the range from 250° to 350° C. and the pressure is preferably in the range from 10 to 50 bars.
  • the GHSV may suitably be in the range from 100 to 20,000 h -1 .
  • the process may be carried out batchwise or continuously in a fixed bed, fluidised bed, moving bed or slurry phase reactor.
  • catalysts produced by the process of the present invention provide low selectivities to methane and carbon dioxide, thereby minimising carbon wastage in the form of undesirable by-products.
  • FIG. 1 shows an apparatus employed in continuous precipitation methods described in Examples below.
  • FIG. 2 shows a plot of hours on stream versus percent CO conversion, CH 4 selectivity and CO 2 selectivity as described below in Example 7.
  • RuCl 3 (H 2 O) x (0.3974 g; 1.52 mmoles) dissolved in distilled water (100 cm 3 ) was added dropwise to a vigorously stirred solution of Ce(NO 3 ) 3 .(H 2 O) 6 (75.40 g; 173.64 mmoles) made up to 750 cm 3 with distilled water.
  • a solution of KNO 3 (1.1421 g; 11.30 mmoles) in distilled water (50 cm 3 ) was then added dropwise to the aqueous ruthenium chloride/cerous nitrate with stirring.
  • the solution containing ruthenium/cerium and potassium was added to freshly prepared aqueous NH 4 HCO 3 (299.7 g; 3.79 mmoles) made up to 2500 cm 3 with distilled water over ca. 1 hour.
  • the pH of the alkali was constant at 8.7-8.8 throughout the precipitation.
  • Stirring was continued for 0.25 h after all of the reagents were added and the mixture was vacuum filtered to yield a light grey sludge and a light yellow filtrate.
  • the sludge was vigorously stirred with distilled water (3000 cm 3 ) for 0.25 h and then vacuum filtered.
  • Example 1 The procedure of Example 1 was repeated except that the pH control during precipitation was inferior to that of Example 1, the pH varying from 8.40-8.65.
  • Example 2 A similar procedure to that of Example 1 was used except that approx. three times the quantity of reagents was used to yield 64.70 g of product gel.
  • the RuCl 3 /Ce(NO 3 ) 3 solution was added to the aqueous NH 4 HCO 3 solution at the rate of 50 cm 3 min -1 .
  • the addition of reagents was therefore completed in approx. the same time period (69 minutes) as the smaller scale preparations of Examples 1 and 2.
  • the pH of the aqueous NH 4 HCO 3 rose from 8.16 to 8.68 during the preparation.
  • 1 is a stainless steel constant head mixing vessel
  • 2 is a precipitant delivery ring
  • 3 is a pipe for delivery of solution containing metals to be precipitated
  • 4 is a paddle stirrer
  • 5 is a pH electrode
  • 6 is an overflow pipe.
  • RuCl 3 (H 2 O) 3 (12.085 g; 46.23 mmoles) was dissolved in distilled water (0.40 liter) and added dropwise to a vigorously stirred solution of Ce(NO 3 ) 3 (H 2 O) 6 (303 g; 0.698 moles) made up to 3 liters with distilled water.
  • a solution of KNO 3 (4.700 g; 46.24 mmoles) in distilled water (0.20 l) was then added dropwise to the aqueous ruthenium chloride/cerous nitrate solution with stirring. This solution is hereinafter referred to as solution A.
  • solution B NH 4 HCO 3 (1.20 kg; 15.18 moles) was dissolved in 10 liters of distilled water. This solution is hereinafter referred to as solution B.
  • solution A was fed through pipe 3 and solution B was fed simultaneously through the precipitant delivery ring 2 to the constant head mixing vessel 1 via peristatic pumps (not shown) at a flow rate ratio sufficient to control the pH in the mixing vessel 1 as measured by the pH electrode 5 between 8.0 and 8.7. Efficient mixing of the solutions A and B was received by rapid rotation of the paddle stirrer 4.
  • the suspended precipitate was constantly bled off via the overflow pipe 6 and filtered on three 5 liter Buchner Funnel/Flasks to yield a light grey solid and a light yellow filtrate.
  • the individual solids were sucked dry on the filter over ca. 2 hours and were left for 17 hours in air. The solids showed some signs of darkening during drying.
  • the solids from the three Buchner Funnels were combined to yield 916.3 g in total.
  • the damp cake was split into two portions C (279.3 g) and D (630 g).
  • Portion D was vigorously stirred with distilled water (2 liters) and filtered. This washing procedure was repeated twice more and finally the solid was vacuum dried (100° C., 17 mm Hg, 17 h) to yield 60.75 g of dried gel.
  • Solution (i) was added to solution (iii).
  • Solution (ii) was added to the mixed solution (i) and (iii).
  • the co-precipitation was effected at a pH between 7.70 and 7.90.
  • the precipitated solid was vacuum filtered to yield a dense metallic silver sludge.
  • the dried solid was washed with (i) 101, (ii) 121 and (iii) 101 of distilled water before drying at 110° C. in air for 17 hours.
  • the dried solid was pressed and heat treated in a manner identical to that described in Example 1.
  • Solution (i) was added to solution (iii).
  • Solution (ii) was added to the mixed solution (i) and (iii).
  • the light grey precipitate produced by the coprecipitation was vacuum filtered and washed three times with 50-551 distilled water.
  • the damp cake so-produced was dried at 110° C. in air for 30 hours.
  • the nitrogen-roasted gel was then mixed with distilled water (0.61 kg -1 ) in a ⁇ Z ⁇ blade mixer. Finally, it was dried at 30° C. in air for 30 h.
  • the powder was crushed and sieved to less than 1 mm and was then dry mixed with stearic acid (2 g acid to 100 g dry gel).
  • the mixture was then pelleted using a Manesty B3B 16 station mulitple punch tablet maker to yield 4.8 mm diameter ⁇ 4.0 mm long cylindrical pellets. These pellets were crushed and sieved to 250-500 ⁇ m before testing.
  • the catalyst maintained its performance during the period 350 HOS to 2,200 HOS.
  • Example 7 Using the catalyst produced in Example 4 in place of the catalyst produced in Example 1 the procedure of Example 7 was repeated except that the catalyst was reduced for 6 h at 305° C. (30 bar H 2 , 111 cm 3 min -1 ). At 47 HOS the catalyst was given a hydrogen treatment by stopping the CO flow for one hour.
  • Example 7 Using the catalyst produced in Example 5 in place of the catalyst produced in Example 1 the procedure of Example 7 was repeated except that the catalyst was reduced for 6 h at 305° C. (30 bar H 2 , 111 cm 3 min -1 ).
  • the temperature was adjusted to 250° C. for ca. 0.5 h and then increased to 270° C. before increasing to 290° C. in 10° C. steps and finally to the operating temperature (ca. 300° C.) in 1° C. steps.

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US9205493B1 (en) * 2011-06-28 2015-12-08 Innova Dynamics, Inc. Production of nanostructures

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GB8519321D0 (en) * 1985-07-31 1985-09-04 British Petroleum Co Plc Catalyst
GB8626532D0 (en) * 1986-11-06 1986-12-10 British Petroleum Co Plc Chemical process
GB9025398D0 (en) * 1990-11-22 1991-01-09 British Petroleum Co Plc Catalyst recovery process
CN100431694C (zh) * 2006-06-08 2008-11-12 苏州大学 嵌埋式钌系变换反应催化剂及其制备方法
CN101632928B (zh) * 2009-08-14 2014-10-01 昆明理工大学 火焰燃烧合成法一步制备nsr催化剂
EP2909142A4 (en) * 2012-10-19 2016-08-31 Basf Se CATALYST FOR THE CONVERSION OF SYNTHESEGAS IN OLEFINE AND MANUFACTURE THEREOF

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GB8600445D0 (en) 1986-02-12
ZA8783B (en) 1988-09-28
AU629955B2 (en) 1992-10-15
WO1987004085A1 (en) 1987-07-16
NZ218840A (en) 1989-01-06
AU5881990A (en) 1990-11-01
CN1011664B (zh) 1991-02-20
AU6844287A (en) 1987-07-28
JPS63502255A (ja) 1988-09-01
CA1265778A (en) 1990-02-13
DE3764106D1 (de) 1990-09-13
AU595853B2 (en) 1990-04-12
EP0232962B1 (en) 1990-08-08
CN87100113A (zh) 1987-08-12
EP0232962A1 (en) 1987-08-19

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